CN104774345B - A kind of method that radiation method prepares filled-type conductive rubber - Google Patents
A kind of method that radiation method prepares filled-type conductive rubber Download PDFInfo
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Abstract
A kind of method that radiation method prepares filled-type conductive rubber, it is related to a kind of method for preparing filled-type conductive rubber.The present invention is to solve co-mixing system uniformity in the emulsion dispersion of current filled-type conductive rubber and the technical problem of stability difference.The method that a kind of radiation method of the present invention prepares filled-type conductive rubber is carried out according to the following steps：First, expanded graphite is peeled off；2nd, it is blended；3rd, electron beam irradiation；4th, it is demulsified.The present invention efficiently solves the problem of filler dispersing uniformity and stability difference in emulsion blending system.
Description
Technical field
The present invention relates to a kind of method for preparing filled-type conductive rubber.
Background technology
Elasticity possessed by elastomeric material is the distinguishing feature of this kind of high polymer material, is not only to its high resiliency at present
Demand, elastomeric material functionalization is always the important development direction in this field, particularly elastomeric material conducting function.Lead
Electric rubber has been obtained for extensive use at numerous aspects such as antistatic product, electronic component and electromagnetic shielding sealing articles.
The most important method for preparing conductive rubber at present is exactly to be filled into be formed in rubber by the method for blending by conductive filler to lead
Electric network, realize its conducting function.Filled-type conductive rubber has easy processing, cost low etc. relative to structural conductive rubber
Feature, the preparation method of filled-type conductive rubber mainly have the methods of melt blending, emulsion blending and solution blending.Current system
Standby technology is mainly the method for melt blending, such as Chinese patent CN103122085A and CN102911411A；Emulsion blending
Method, such as Chinese patent 103289138A and 103183847A；The method of solution blending, such as Chinese patent
CN102674324A and CN104130753A.The subject matter that composite is prepared using melt blending is packing specific area
Larger, surface energy is higher, and this can cause filler to cause to assemble in polymeric matrix, causes its dispersiveness poor；In addition, rubber
Melt viscosity is larger, and mixed refining process is more difficult.Using the method for solution blending can solve the problem that rubber melt viscosity it is larger, be kneaded plus
The problem of work difficulty, but it can cause environmental pollution, and difficult solvent recovery, and it is higher to prepare cost.The side of emulsion blending
Method has obvious advantage, and processing is easier to, and will not pollute, although latex particle can be made to be filled out with conduction in demulsification
Expect co-coagulation, the scattered uniformity of conductive filler is preferable, but because latex and filler interphase interaction are smaller, between latex particle with
Reassociating between filler be still difficult to avoid that, therefore solves emulsion blending and prepare conductive material and co-mixing system uniformity and stably
Sex chromosome mosaicism is the technical bottleneck of this area all the time.
The content of the invention
The present invention is to solve co-mixing system uniformity and stability in the emulsion dispersion of current filled-type conductive rubber
The technical problem of difference, and a kind of method that radiation method prepares filled-type conductive rubber is provided.
The method that a kind of radiation method of the present invention prepares filled-type conductive rubber is carried out according to the following steps：
First, expanded graphite is peeled off：With micro-wave oven to expanded graphite microwave radiation 30s~40s, surface-active is then placed in
In the agent aqueous solution, ultrasonic 20h~24h, nano graphite flakes aqueous emulsion is obtained；The mass concentration of described aqueous surfactant solution
For 3 ‰~5 ‰；The mass concentration of expanded graphite is 0.6 ‰~2 ‰ in described nano graphite flakes aqueous emulsion；
2nd, it is blended：The nano graphite flakes aqueous emulsion that step 1 obtains is added in latax, ultrasonic 30min~
40min, obtain blended liquid；The mass ratio 1 of the solute in the latax described in expanded graphite and step 2 described in step 1:(5
~200)；
3rd, electron beam irradiation：The blended liquid that step 2 is obtained is encapsulated into polythene film bag, is in energy
1.2MeV, beam intensity are that 0.05mA~1mA and irradiation dose carry out electron beam irradiation under conditions of 10kGy~150kGy,
Obtain mixed liquor；
4th, it is demulsified：CaCl is added in the mixed liquor obtained under conditions of ultrasound to step 32The aqueous solution, flocculated
Thing, then filter, dry 3h~4h under conditions of being 100 DEG C in temperature, tabletting, obtain the filled-type conduction rubber of radiation method preparation
Glue；Described CaCl2The mass concentration of the aqueous solution is 1%~1.5%；Described CaCl2The mixing that the aqueous solution obtains with step 3
The volume ratio of liquid is 1:7.5.
The present invention by expansible graphite it is microwaved after, be added in aqueous surfactant solution and infiltrate, through ultrasound at
Obtain peeling off the graphite flake aqueous emulsion for nanoscale after reason, and add it in rubber latex liquid, then through ultrasonic disperse at
Electron beam radiation treatment is used after reason, latex particle finally is made using electrolyte solution demulsification interacts what is mixed with nano graphite flakes
Conductive rubber.
In the present invention, because electron beam irradiation increases the degree of cross linking of latex particle, latex particle aggregation tendency reduces,
Thus, particle keeps the ability of its intrinsic form to improve；Meanwhile under the conditions of x ray irradiation x, not only produce latex particle surface
Liveliness proof center, also makes to produce activated centre on the nano graphite flakes surface of suspended state that (and the sp2 of graphite can also make in activity
The heart is more stable) be bonded so that latex particle and nano graphite flakes are formed, therefore, after demulsification can obtain it is finely divided, have mutually
Effect and orderly floccule, it is made conductive rubber through filtering, after drying and tabletting again, efficiently solves emulsion blending system
The problem of middle filler dispersing uniformity and stability difference.
Conductive filler of the present invention is to peel off receiving for preparation by ultrasound using after the heated expansion of expansible graphite
Rice graphite flake, the conductive rubber are dispersed in rubber matrix and obtained in order by radiation treatment to be partially stripped nano graphite flakes
Distribution and form interaction, turn into the network structure that latex particle is wrapped in nano graphite flakes.
Latax of the present invention can directly bought on the market, be had per money latax to one's name special
Some trades mark, the mass concentration of latax is fixed corresponding to each trade mark.
Brief description of the drawings
Fig. 1 is thermogravimetric curve figure, and the filled-type conductive rubber that curve 1 is prepared for experiment one, curve 2 is that experiment two obtains
Radiation method prepare filled-type conductive rubber；
Fig. 2 is absorbance curve figure, and it is the dilution of FM301 XNBRs latax to the trade mark in experiment three that curve 1, which is,
The absorbance curve measured after to 280 times, curve 2 is diluted for the obtained blended liquid of one step 2 of experiment so that the wherein trade mark
The absorbance curve measured after 280 times is diluted to for the mass concentration of FM301 XNBR lataxes, curve 3 is experiment
The mixed liquor that two step 3 obtain, which is diluted, make it that wherein the trade mark is dilute for the mass concentration of FM301 XNBR lataxes
Release the absorbance curve measured after 280 times；
Fig. 3 is electron beam irradiation amount-specific insulation graph of a relation, and curve 1 is experiment one, tests two, tests 11, examination
The curve of conductive rubber fitting prepared by 12, experiment 13, experiment 14 and experiment 15 is tested, curve 2 is experiment five, experiment
4th, the curve of gum material fitting prepared by experiment six, experiment seven, experiment eight, experiment nine and experiment ten.
Embodiment
Embodiment one：Present embodiment is a kind of method that radiation method prepares filled-type conductive rubber, is specifically
Carry out according to the following steps：
First, expanded graphite is peeled off：With micro-wave oven to expanded graphite microwave radiation 30s~40s, surface-active is then placed in
In the agent aqueous solution, ultrasonic 20h~24h, nano graphite flakes aqueous emulsion is obtained；The mass concentration of described aqueous surfactant solution
For 3 ‰~5 ‰；The mass concentration of expanded graphite is 0.6 ‰~2 ‰ in described nano graphite flakes aqueous emulsion；
2nd, it is blended：The nano graphite flakes aqueous emulsion that step 1 obtains is added in latax, ultrasonic 30min~
40min, obtain blended liquid；The mass ratio 1 of the solute in the latax described in expanded graphite and step 2 described in step 1:(5
~200)；
3rd, electron beam irradiation：The blended liquid that step 2 is obtained is encapsulated into polythene film bag, is in energy
1.2MeV, beam intensity are that 0.05mA~1mA and irradiation dose carry out electron beam irradiation under conditions of 10kGy~150kGy,
Obtain mixed liquor；
4th, it is demulsified：CaCl is added in the mixed liquor obtained under conditions of ultrasound to step 32The aqueous solution, flocculated
Thing, then filter, dry 3h~4h under conditions of being 100 DEG C in temperature, tabletting, obtain the filled-type conduction rubber of radiation method preparation
Glue；Described CaCl2The mass concentration of the aqueous solution is 1%~1.5%；Described CaCl2The mixing that the aqueous solution obtains with step 3
The volume ratio of liquid is 1:7.5.
Embodiment two：Present embodiment is unlike embodiment one：Surface described in step 1
Surfactant is in neopelex, dodecyl sodium sulfate, polysorbate60 and Tween 80 in aqueous surfactant solutions
One or more of mixtures.It is other identical with embodiment one.
Embodiment three：Present embodiment is unlike embodiment two：Micro-wave oven described in step 1
Power be 900W.It is other identical with embodiment two.
Embodiment four：Present embodiment is unlike embodiment two：Latax described in step 2
For caoutchouc latex liquid, butadiene-styrene rubber latax, butadiene rubber latax, ACM latax, neoprene breast
One or more of mixtures in glue, nitrile rubber latax and XNBR latax.Other and specific implementation
Mode two is identical.
Embodiment five：Present embodiment is unlike embodiment one：Step 2 is obtained in step 3
To blended liquid be encapsulated into polythene film bag, energy be 1.2MeV, beam intensity be 0.2mA~0.6mA and irradiation agent
Amount carries out electron beam irradiation under conditions of 70kGy~100kGy, obtains mixed liquor.It is other identical with embodiment one.
Using following verification experimental verifications effect of the present invention：
Experiment one：This experiment is contrast test, is specifically carried out according to the following steps：
First, expanded graphite is peeled off：With micro-wave oven to expanded graphite microwave radiation 35s, surfactant water is then placed in
In solution, ultrasonic 24h, nano graphite flakes aqueous emulsion is obtained；The mass concentration of described aqueous surfactant solution is 3.5 ‰；
The mass concentration of expanded graphite is 0.7 ‰ in described nano graphite flakes aqueous emulsion；
2nd, it is blended：The nano graphite flakes aqueous emulsion that step 1 obtains is added in latax, ultrasonic 30min, is total to
Mixed liquid；The mass ratio 1 of the solute in the latax described in expanded graphite and step 2 described in step 1:100；
3rd, it is demulsified：CaCl is added in the blended liquid obtained under conditions of ultrasound to step 22The aqueous solution, flocculated
Thing, then filter, dry 3h under conditions of being 100 DEG C in temperature, tabletting, obtain filled-type conductive rubber；Described CaCl2Water
The mass concentration of solution is 1%；Described CaCl2The volume ratio for the mixed liquor that the aqueous solution obtains with step 3 is 1:7.5.
The model 8099300 of expanded graphite described in step 1；Aqueous surfactant solution described in step 1
Middle surfactant is neopelex；The power of micro-wave oven described in step 1 is 900W；Breast described in step 2
Glue is that the trade mark is FM301 XNBR lataxes.
Experiment two：This experiment is a kind of method that radiation method prepares filled-type conductive rubber, is specifically entered according to the following steps
Capable：
First, expanded graphite is peeled off：With micro-wave oven to expanded graphite microwave radiation 35s, surfactant water is then placed in
In solution, ultrasonic 24h, nano graphite flakes aqueous emulsion is obtained；The mass concentration of described aqueous surfactant solution is 3.5 ‰；
The mass concentration of expanded graphite is 0.7 ‰ in described nano graphite flakes aqueous emulsion；
2nd, it is blended：The nano graphite flakes aqueous emulsion that step 1 obtains is added in latax, ultrasonic 30min, is total to
Mixed liquid；The mass ratio 1 of the solute in the latax described in expanded graphite and step 2 described in step 1:100；
3rd, electron beam irradiation：The blended liquid that step 2 is obtained is encapsulated into polythene film bag, is in energy
1.2MeV, beam intensity are that 0.25mA and irradiation dose carry out electron beam irradiation under conditions of 50kGy, obtain mixed liquor；
4th, it is demulsified：CaCl is added in the mixed liquor obtained under conditions of ultrasound to step 32The aqueous solution, flocculated
Thing, then filter, dry 3h under conditions of being 100 DEG C in temperature, tabletting, obtain the filled-type conductive rubber of radiation method preparation；
Described CaCl2The mass concentration of the aqueous solution is 1%；Described CaCl2The volume ratio for the mixed liquor that the aqueous solution obtains with step 3
For 1:7.5；
Surfactant is neopelex in aqueous surfactant solution described in step 1；Step 1 institute
The power for the micro-wave oven stated is 900W；Latax described in step 2 is that the trade mark is FM301 XNBR lataxes.
Fig. 1 is thermogravimetric curve figure, and the filled-type conductive rubber that curve 1 is prepared for experiment one, curve 2 is that experiment two obtains
Radiation method prepare filled-type conductive rubber, as can be seen from the figure test two in irradiate 50kGy electron beams conductive rubber
Heat endurance improves, and the temperature of weightlessness 5% improves 8 DEG C, improves 4.5 DEG C during weightlessness 10%.
Experiment three：It is that FM301 XNBRs latax dilutes 280 times to the trade mark under conditions of wavelength is 480nm
Absorbance test is carried out afterwards；The blended liquid that one step 2 of experiment obtains is diluted so that wherein the trade mark is FM301 carboxyl fourths
The mass concentration of solute dilutes 280 times in nitrile rubber latax, then carries out absorbance test；That tests that two step 3 obtain is mixed
Close liquid and be diluted and make it that wherein the trade mark is that the mass concentration of solute in FM301 XNBR lataxes dilutes 280 times, so
Absorbance test is carried out afterwards.
Fig. 2 is absorbance curve figure, and it is the dilution of FM301 XNBRs latax to the trade mark in experiment three that curve 1, which is,
The absorbance curve measured after to 280 times, curve 2 is diluted for the obtained blended liquid of one step 2 of experiment so that the wherein trade mark
The absorbance curve measured after 280 times is diluted for the mass concentration of solute in FM301 XNBR lataxes, curve 3 is
Test the mixed liquor that two step 3 obtain and be diluted and make it that wherein the trade mark is solute in FM301 XNBR lataxes
Mass concentration dilutes the stability highest of the absorbance curve, as can be seen from the figure pure latex that are measured after 280 times, adds graphite
Its bad stability afterwards, after blended liquid is irradiated into 50kGy electron beams, latex system stability is worst, illustrates that irradiation can make
Interaction enhanced between latex particle and graphite and settle down jointly, therefore absorbance is minimum, latex particle and graphite
Between Interaction enhanced the stability of final finished conductive rubber can be caused to strengthen.
Experiment four：This experiment is contrast test, is specifically carried out according to the following steps：
First, electron beam irradiation：Latax is encapsulated into polythene film bag, energy be 1.2MeV, beam intensity be
0.25mA and irradiation dose carry out electron beam irradiation under conditions of 10kGy, obtain mixed liquor；
2nd, it is demulsified：CaCl is added in the mixed liquor obtained under conditions of ultrasound to step 12The aqueous solution, flocculated
Thing, then filter, dry 3h under conditions of being 100 DEG C in temperature, tabletting, obtain gum material；Described CaCl2The aqueous solution
Mass concentration be 1%；Described CaCl2The volume ratio for the mixed liquor that the aqueous solution obtains with step 1 is 1:7.5.
Latax described in step 1 is that the trade mark is FM301 XNBR lataxes.
Experiment five：This experiment is contrast test, is specifically carried out according to the following steps：
First, it is demulsified：CaCl is added into latax under conditions of ultrasound2The aqueous solution, flocculate is obtained, is then filtered,
3h is dried under conditions of being 100 DEG C in temperature, tabletting, obtains gum material；Described CaCl2The mass concentration of the aqueous solution is
1%；Described CaCl2The volume ratio of the aqueous solution and latax is 1:7.5；Latax described in step 1 is that the trade mark is FM301
XNBR latax.
Experiment six：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment four
30kGy is other identical with experiment four.
Experiment seven：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment four
50kGy is other identical with experiment four.
Experiment eight：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment four
70kGy is other identical with experiment four.
Experiment nine：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment four
100kGy is other identical with experiment four.
Experiment ten：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment four
150kGy is other identical with experiment four.
Test 11：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment two
10kGy is other identical with experiment four.
Test 12：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment two
30kGy is other identical with experiment four.
Test 13：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment two
70kGy is other identical with experiment four.
Test 14：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment two
100kGy is other identical with experiment four.
Test 15：This experiment is contrast test, and this experiment is from the irradiation dose of step 1 unlike experiment two
150kGy is other identical with experiment four.
Fig. 3 is electron beam irradiation amount-specific insulation graph of a relation, and curve 1 is experiment one, tests two, tests 11, examination
The curve of conductive rubber fitting prepared by 12, experiment 13, experiment 14 and experiment 15 is tested, curve 2 is experiment five, experiment
4th, the curve of gum material fitting prepared by experiment six, experiment seven, experiment eight, experiment nine and experiment ten, can from figure
Go out, irradiation can simply cause the change of the less specific insulation of gum material, and add the composite of expanded graphite
In no electron beam irradiation, its specific insulation reduces 1 order of magnitude, illustrates that it has formd certain conductive path, but
The specific insulation of composite is greatly improved after electron beam irradiation, improves nearly 4 orders of magnitude, explanation
Graphite flake has been obtained further finely divided and has been uniformly distributed in co-mixing system, just causes the specific insulation of composite to carry
Gao Liao.
Claims (4)
1. a kind of method that radiation method prepares filled-type conductive rubber, it is characterised in that radiation method prepares filled-type conductive rubber
Method is carried out according to the following steps：
First, expanded graphite is peeled off：With micro-wave oven to expanded graphite microwave radiation 30s~40s, surfactant water is then placed in
In solution, ultrasonic 20h~24h, nano graphite flakes aqueous emulsion is obtained；The mass concentration of described aqueous surfactant solution is
3 ‰~5 ‰；The mass concentration of expanded graphite is 0.6 ‰~2 ‰ in described nano graphite flakes aqueous emulsion；
2nd, it is blended：The nano graphite flakes aqueous emulsion that step 1 obtains is added in latax, ultrasonic 30min~40min, obtained
To blended liquid；The mass ratio 1 of the solute in the latax described in expanded graphite and step 2 described in step 1:(5~200)；
Described latax is caoutchouc latex liquid, butadiene-styrene rubber latax, butadiene rubber latax, ACM latex
One or more of mixtures in liquid, neoprene latax, nitrile rubber latax and XNBR latax；
3rd, electron beam irradiation：The blended liquid that step 2 is obtained is encapsulated into polythene film bag, is 1.2MeV, beam in energy
Intensity of flow is that 0.05mA~1mA and irradiation dose carry out electron beam irradiation under conditions of 10kGy~150kGy, is mixed
Liquid；
4th, it is demulsified：CaCl is added in the mixed liquor obtained under conditions of ultrasound to step 32The aqueous solution, flocculate is obtained, so
After filter, temperature be 100 DEG C under conditions of dry 3h~4h, tabletting, obtain radiation method preparation filled-type conductive rubber；Institute
The CaCl stated2The mass concentration of the aqueous solution is 1%~1.5%；Described CaCl2The mixed liquor that the aqueous solution obtains with step 3
Volume ratio is 1:7.5.
2. the method that a kind of radiation method according to claim 1 prepares filled-type conductive rubber, it is characterised in that step 1
Described in aqueous surfactant solution in surfactant be neopelex, dodecyl sodium sulfate, polysorbate60
With one or more of mixtures in Tween 80.
3. the method that a kind of radiation method according to claim 1 prepares filled-type conductive rubber, it is characterised in that step 1
The power of described micro-wave oven is 900W.
4. the method that a kind of radiation method according to claim 1 prepares filled-type conductive rubber, it is characterised in that step 3
The middle blended liquid for obtaining step 2 is encapsulated into polythene film bag, energy be 1.2MeV, beam intensity be 0.2mA~
0.6mA and irradiation dose carry out electron beam irradiation under conditions of 70kGy~100kGy, obtain mixed liquor.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445646A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of polymeric based carbon nano tube composite material in the technical field of nano-materials |
| CN101463149A (en) * | 2007-12-19 | 2009-06-24 | 北京化工大学 | Preparation of wear resistant rubber composite material |
| CN101717520A (en) * | 2009-11-25 | 2010-06-02 | 黑龙江省科学院技术物理研究所 | Method for using electron beam to irradiate crosslinked thermoplastic polyester elastomer |
| CN102532629A (en) * | 2011-12-30 | 2012-07-04 | 北京化工大学 | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material |
| WO2014093139A1 (en) * | 2012-12-14 | 2014-06-19 | 3M Innovative Properties Company | Method of polymerizing ethylenically-unsaturated materials using ionizing radiation |
-
2015
- 2015-04-27 CN CN201510204889.XA patent/CN104774345B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463149A (en) * | 2007-12-19 | 2009-06-24 | 北京化工大学 | Preparation of wear resistant rubber composite material |
| CN101445646A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of polymeric based carbon nano tube composite material in the technical field of nano-materials |
| CN101717520A (en) * | 2009-11-25 | 2010-06-02 | 黑龙江省科学院技术物理研究所 | Method for using electron beam to irradiate crosslinked thermoplastic polyester elastomer |
| CN102532629A (en) * | 2011-12-30 | 2012-07-04 | 北京化工大学 | Preparation method of completely peeled oxidation graphene/ rubber nanometer composite material |
| WO2014093139A1 (en) * | 2012-12-14 | 2014-06-19 | 3M Innovative Properties Company | Method of polymerizing ethylenically-unsaturated materials using ionizing radiation |
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